The year 2020 is a landmark in polymer chemistry, as it is the 100th anniversary of Hermann Staudinger’s paper “tiber Polymerisation”（H.Staudinger,Chem.Ber.1920,531，1073-1085). Every topic covered in this text reflects the tremendous strides in knowledge initiated by Staudinger's “macromolecular hypothesis.” The global polymer industry is estimated to be worth almost half a trillion US dollars annually, so progress in the field has been at least as meteoric in technology as in fundamental science. Polymer chemistry has established itself as a major component of modern academic chemistry, while enjoying a growing presence in diverse fields, including materials science, chemical engineering, biomedical engineering, mechanical engineering, and physics, to cite a few.
This edition retains both the underlying philosophy and the overall structure of its predecessor. The emphasis is on fundamental, universal principles, which apply across a wide range of macromolecular systems. The text is intended for students in a variety of fields, especially those identified above, with the assumption of prior courses in organic and physical chemistry. Important mathematical relations are almost all derived in detail, although of course the derivations can be by-passed on a first reading. Necessary concepts from other fields, such as statistics and probability, thermodynamics, wave propagation, and mechanics of fluids and solids, are introduced as needed.
The text is suitable for a full year, graduate-level course, but may be used for semester-long courses by emphasizing subsections. It can also be used for upper-level undergraduate courses, with appropriate omissions. After an introductory chapter, there are three blocks of four chapters， emphasizing synthesis, solution properties, and bulk properties, respectively.

Completion of this edition has been greatly facilitated by the input and efforts of many people. I would particularly like to thank my colleagues at the University of Minnesota, who have provided at various times much needed encouragement，helpful examples，problem suggestions，and technical corrections and improvements: Frank Bates, Phil Biihlmann, Michelle Calabrese, Kevin Dorfman, Chris Ellison, Marc Hillmyer, Tom Hoye, Chris Macosko, Mahesh Mahanthappa, David Morse, Theresa Reineke, and Ilja Siepmann. Members of my research group carefully proofread drafts of the revised chapters, and provided multiple suggestions for improving clarity: McKenzie Coughlin, Nayereh Dadoo, S. Piril Ertem, Hiro Hasegawa, Joe Hassler, Yuuki Hirose, Aakriti Kharel, Lucy Liberman, Aaron Lindsay, Pranati Mondkar, Svetlana Morozova, Emmanuel Onuoha, Sarah Seeger, Claire Seitzinger, Donny Shen, Jimin Shim, Michael Sims, Julia Early, Nicholas Van Zee, En Wang, Shuyi Xie, Bo Zhang, Wenjia Zhang, Caini Zheng, and Jiahao Zhu. I am indebted to colleagues around the country who have used the text and caught various errors, and/or raised probing questions about the technical content: Nitash Balsara, Christopher Bates, Chris Bowman,Franklin Chen, Shaw Chen, Russ Composto, Steve Craig, Mark Ediger, Ryan Hayward, Sangwoo Lee, Jane Lipson, Darren Lipomi, Joe Lott, Nate Lynd, Michael Mackay, Scott Milner, Chang Ryu, Charles Schroeder, Rachel Segalman, Vivek Sharma, Lynn Walker, Shiqing Wang, Ryszard Wycisk, Arun Yethiraj, and Alex Zhukhovitskiy.
As a textbook, feedback from students is especially valuable. Over the intervening years since publication of the second edition, I have had the opportunity to teach a graduate-level polymer class, Chemistry/Materials Science 8211, on five occasions. I appreciate all the questions, comments, and suggestions from the participants: Jun Ai, Carlos Alfonzo, Mark Amendt, Erin Arndt, Zhifeng Bai, Cody Beam, Charles Beaman, Sisir Bhattacharya, Josh Casey, Li Chen, Soo-Hyung Choi, Adelyn Crabtree, Nathan Craig, Rishad Dalai, Carmelo Declet-Perez, Claire Dingwell, William Drasler, Matthew Dubay, Sarit Dutta, Audrey Eigner, Jack Elder, David Ellison, Ashish Gaikwad, Tim Gillard, Ethan Gormong, William Gramlich, Yuanyan Gu, Brian Habersberger, Karen Haman, Jing Han, Aaron Hedegaard, Liz Jackson, Mi Young Jeon, Mengyuan Jin, Brad Jones, Brynna Jones, Vivek Kalihari, Sreeram Kalpathy, Shashank Kamdar, Moon Sung Kang, Jun Kang, Sangwon Kim, Isha Koonar, Secil Koseoglu, Whitney Kruse, Nabil Laachi, Maggie Lau, Intaek Lee, Keun-Hyung Lee, Han Lee, Yu Lei, Kirby Liao, Stephanie Liffland, Chun Liu, Jennifer Lowe, Lian Luo, Zixue Ma, Ameara Mansour, Mark Martello, Luca Martinetti, Amanda Maxwell, Lucas McIntosh, Pavani Medapuram，Nicholas Michaelson，Andreas Mueller，Leslie O’Leary, Eric Olson, Emmanuel Onuoha, Chang-yub Paek, Sanshui Pan, Todd Pangburn, Jong Hyuk Park, Walter Partlo, Xiayu Peng, Matt Petersen, Jason Peterson, Louis Pitet, Kevin Pustulka, Yuqiang Qian, Chandrasekhar Ramasubramanian, Aruna Ramkrishnan, Erica Redline, Jeremiah Riesberg, Marc Rodwogin, Claire Seitzinger, Zhengyuan Shen, Zahra Sohrabpour, Jie Song, Josh Speros, Derek Stevens, Dawud Tan, Suqin Tan, Rajiv Taribagil, Grace Theryo, Raghuram Thiagarajan, Nicholas Van Zee, Kumar Varoon, Anh Vu, Yun-Yan Wang, Lynn Wolf, James Wydra, Jie Xi, Han Xiao, Ligeng Yin, Bokyung Yoon, Jingwen Zhang, Sipei Zhang, Bo Zhang, Can Zhou, and Xu Zou.
Three individuals merit special acknowledgment. Joe Hexum was of great assistance in manipulating and improving my clumsy Powerpoint illustrations. He also did yeoman^ work in securing necessary permissions for reprinting figures. A great deal of the writing and editing of this edition took place during a four-month sabbatical with Michael Rubinstein and his group at Duke University. Beyond gracious hospitality, Michael also allowed me to sit in on his own polymer physics class, which I found to be consistently thought-provoking and stimulating. Finally, my spouse, Dr. Susanna Amelar Lodge, spent many weeks extracting data from the literature and carefully recreating graphs, which constitute the majority of the figures in this edition. She also has provided consistent encouragement and support in all my professional ventures.

Preface to the Third Edition xiii

Chapter 1 Introduction to Chain Molecules 1

1.1 Introduction 1

1.2 How Big is Big? 3

      1.2.1 Molecular Weight 3

      1.2.2 Spatial Extent 5

1.3 Linear and Branched Polymers, Homopolymers, and Copolymers 7

      1.3.1 Branched Structures 7

      1.3.2 Copolymers 8

1.4 Addition, Condensation, and Naturally Occurring Polymers 10

      1.4.1 Addition and Condensation Polymers 11

      1.4.2 Natural Polymers 13

1.5 Polymer Nomenclature 18

1.6 Structural Isomerism 20

      1.6.1 Positional Isomerism 20

      1.6.2 Stereo Isomerism 21

      1.6.3 Geometrical Isomerism 23

1.7 Molecular Weights and Molecular Weight Averages 25

      1.7.1 Number-, Weight-, and z-Average Molecular Weights 25

      1.7.2 Dispersity and Standard Deviation 27

      1.7.3 Examples of Distributions 29

1.8 Measurement of Molecular Weight 31

      1.8.1 General Considerations 31

      1.8.2 End Group Analysis 32

      1.8.3 MALDI Mass Spectrometry 34

1.9 Preview of Things to Come 36

1.10 Chapter Summary 37

Problems 38

References 40

Further Readings .41

Chapter 2 Step-Growth Polymerization 43

2.1 Introduction 43

2.2 Condensation Polymers: One Step at a Time 43

      2.2.1 Classes of Step-Growth Polymers 43

      2.2.2 A First Look at the Distribution of Products 44

      2.2.3 A First Look at Reactivity and Reaction Rates 46

2.3 Kinetics of Step-Growth Polymerization 49

      2.3.1 Catalyzed Step-Growth Reactions 50

      2.3.2 How Should Experimental Data Be Compared with Theoretical Rate Laws? 51

      2.3.3 Uncatalyzed Step-Growth Reactions 53

2.4 Distribution of Molecular Sizes 56

      2.4.1 Mole Fractions of Species 57

      2.4.2 Weight Fractions of Species 58

2.5 Polyesters 61

2.6 Polyamides 65

2.7 Other Examples of Important Step-growth Polymers 68

      2.7.1 Polycarbonates 68

      2.7.2 Polyimides 69

      2.7.3 Polyurethanes 69

      2.7.4 Polysiloxanes 70

      2.7.5 Polythiophenes 71

2.8 Stoichiometric Imbalance 71

2.9 Chapter Summary 75

Problems 76

References 82

Further Readings 82

Chapter 3 Chain-Growth Polymerization 83

3.1 Introduction 83

3.2 Chain-Growth and Step-Growth Polymerizations: Some Comparisons 83

3.3 Initiation 85

      3.3.1 Initiation Reactions 86

      3.3.2 Fate of Free Radicals 87

      3.3.3 Kinetics of Initiation 89

      3.3.4 Temperature Dependence of Initiation Rates 91

3.4 Termination 92

      3.4.1 Combination and Disproportionation 92

      3.4.2 Effect of Termination on Conversion to Polymer 94

      3.4.3 Steady-State Radical Concentration 95

3.5 Propagation 97

      3.5.1 Rate Laws for Propagation 97

      3.5.2 Temperature Dependence of Propagation Rates 99

      3.5.3 Kinetic Chain Length 101

3.6 Radical Lifetime 103

3.7 Distribution of Molecular Weights 106

      3.7.1 Distribution of i-mers: Termination by Disproportionation 106

      3.7.2 Distribution of /-mers: Termination by Combination 109

3.8 Chain Transfer 111

      3.8.1 Chain Transfer Reactions 111

      3.8.2 Evaluation of Chain Transfer Constants 113

      3.8.3 Chain Transfer to Polymer 115

      3.8.4 Suppressing Polymerization 116

3.9 Chapter Summary 117

Problems 118

References 124

Further Readings 124

Chapter 4 Controlled Polymerization 125

4.1 Introduction 125

4.2 Poisson Distribution for an Ideal Living Polymerization 126

      4.2.1 Kinetic Scheme 127

      4.2.2 Breadth of the Poisson Distribution 130

4.3 Anionic Polymerization 134

4.4 Block Copolymers, End-Functional Polymers, and Branched Polymers by Anionic Polymerization 138

      4.4.1 Block Copolymers 138

      4.4.2 End-Functional Polymers 142

      4.4.3 Regular Branched Architectures 144

4.5 Cationic Polymerization 147

      4.5.1 Aspects of Cationic Polymerization 147

      4.5.2 Living Cationic Polymerization 150

4.6 Controlled Radical Polymerization 152

      4.6.1 General Principles of Controlled Radical Polymerization 153

      4.6.2 Particular Realizations of Controlled Radical Polymerization 154

      4.6.2.1 Atom Transfer Radical Polymerization (ATRP) 155

      4.6.2.2 Stable Free-Radical Polymerization (SFRP) 156

      4.6.2.3 Reversible Addition-Fragmentation Chain-Transfer (RAFT) Polymerization 157

4.7 Polymerization Equilibrium 160

4.8 Ring-Opening Polymerization (ROP) 163

      4.8.1 General Aspects 163

      4.8.2 Specific Examples of Living Ring-Opening Polymerizations 165

      4.8.2.1 Poly(ethylene oxide) 165

      4.8.2.2 Polylactide 166

      4.8.2.3 Poly(dimethylsiloxane) 167

      4.8.2.4 Ring-Opening Metathesis Polymerization (ROMP) 168

4.9 Dendrimers 169

4.10 Chapter Summary 173

Problems 174

References 176

Further Readings 177

Chapter 5 Copolymers, Microstructure, and Stereoregularity 179

5.1 Introduction 179

5.2 Copolymer Composition 180

      5.2.1 Rate Laws 180

      5.2.2 Composition versus Feedstock 182

5.3 Reactivity Ratios 185

      5.3.1 Effects of r Values 185

      5.3.2 Relation of Reactivity Ratios to Chemical Structure 187

5.4 Resonance and Reactivity 189

5.5 A Closer Look at Microstructure 194

      5.5.1 Sequence Distributions 195

      5.5.2 Terminal and Penultimate Models 199

5.6 Copolymer Composition and Microstructure: Experimental Aspects 201

      5.6.1 Evaluating Reactivity Ratios from Composition Data 201

      5.6.2 Spectroscopic Techniques 203

      5.6.3 Sequence Distribution: Experimental Determination 205

5.7 Characterizing Stereoregularity 209

5.8 A Statistical Description of Stereoregularity 212

5.9 Assessing Stereoregularity by Nuclear Magnetic Resonance 216

5.10 Ziegler—Natta Catalysts 221

5.11 Single-Site Catalysts 224

5.12 Chapter Summary 227

Problems 228

References 232

Further Readings 233

Chapter 6 Polymer Conformations 235

6.1 Conformations, Bond Rotation, and Polymer Size 235

6.2 Average End-to-End Distance for Model Chains 237

      Case 6.2.1 The Freely Jointed Chain 238

      Case 6.2.2 The Freely Rotating Chain 239

      Case 6.2.3 Hindered Rotation Chain 241

6.3 Characteristic Ratio and Statistical Segment Length 241

6.4 Semiflexible Chains and the Persistence Length 245

      6.4.1 Persistence Length of Flexible Chains 246

      6.4.2 Worm-Like Chains 247

6.5 Radius of Gyration 249

6.6 Distributions for End-to-End Distance and Segment Density 254

      6.6.1 Distribution of the End-to-End Vector 255

      6.6.2 Distribution of the End-to-End Distance 257

      6.6.3 Distribution about the Center of Mass 258

6.7 Spheres, Rods, Coils, and Chain Overlap 261

6.8 Self-Avoiding Chains: A First Look 263

6.9 Chapter Summary 264

Problems 265

References 269

Further Readings 269

Chapter 7 Thermodynamics of Polymer Mixtures 271

7.1 Review of Thermodynamic and Statistical Thermodynamic Concepts 271

7.2 Regular Solution Theory 273

      7.2.1 Regular Solution Theory: Entropy of Mixing 274

      7.2.2 Regular Solution Theory: Enthalpy of Mixing 276

7.3 Flory-Huggins Theory 278

      7.3.1 Flory-Huggins Theory: Entropy of Mixing by a Quick Route 279

      7.3.2 Flory-Huggins Theory: Entropy of Mixing by a Longer Route 280

      7.3.3 Flory-Huggins Theory: Enthalpy of Mixing 282

      7.3.4 Flory-Huggins Theory: Summary of Assumptions 283

7.4 Osmotic Pressure 283

      7.4.1 Osmotic Pressure: General Case 284

      7.4.2 Osmotic Pressure: Flory-Huggins Theory 289

7.5 Phase Behavior of Polymer Solutions 291

      7.5.1 Overview of the Phase Diagram 291

      7.5.2 Finding the Binodal 294

      7.5.3 Finding the Spinodal 295

      7.5.4 Finding the Critical Point 296

      7.5.5 Phase Diagram from Flory-Huggins Theory 298

7.6 Flory-Huggins Theory for Binary Polymer Blends 302

7.7 Whafs in X? 304

      7.7.1 X from Regular Solution Theory 304

      7.7.2 X from Experiment 307

      7.7.3 Further Approaches to/ 308

7.8 Excluded Volume and Chains in a Good Solvent 310

7.9 Chapter Summary 314

Problems 315

References 324

Further Readings 324

Chapter 8 Light Scattering by Polymer Solutions 325

8.1 Introduction: Light Waves 325

      Basic Concepts of Scattering 327

8.2 Basic Concepts of Scattering 328

      8.2.1 Scattering from Randomly Placed Objects 328

      8.2.2 Scattering from a Perfect Crystal 328

      8.2.3 Origins of Incoherent and Coherent Scattering 329

      8.2.4 Bragg’s Law and the Scattering Vector 330

8.3 Scattering by an Isolated Small Molecule 332

8.4 Scattering from a Dilute Polymer Solution 334

8.5 The Form Factor and the Zimm Equation 340

      8.5.1 Mathematical Expression for the Form Factor 341

      8.5.2 Form Factor for Isotropic Solutions 343

      8.5.3 Form Factor as qRg-^0 344

      8.5.4 Zimm Equation 344

      8.5.5 Zimm Plot 345

8.6 Scattering Regimes and Particular Form Factors 348

8.7 Experimental Aspects of Light Scattering 350

      8.7.1 Instrumentation 351

      8.7.2 Calibration 353

      8.7.3 Samples and Solutions 354

      8.7.4 Refractive Index Increment 355

8.8 Introduction to Small-Angle Neutron Scattering 355

      8.8.1 Basics of the SANS Process and SANS Instrumentation 356

      8.8.2 SANS from Polymer Blends 360

      Case 8.8.1 An Isotope Blend 361

      Case 8.8.2 A Non-interacting Binary Blend 363

      Case 8.8.3 A Binary Blend with Interactions 364

8.9 Chapter Summary 366

Problems 366

References 376

Further Readings 376

Chapter 9 Dynamics of Dilute Polymer Solutions 377

9.1 Introduction: Friction and Viscosity 377

9.2 Stokes’ Law and Einstein’s Law 381

      9.2.1 Viscous Forces on Rigid Spheres 381

      9.2.2 Suspension of Spheres 382

9.3 Intrinsic Viscosity 385

      9.3.1 General Considerations 385

      9.3.2 Mark—Houwink Equation 386

      9.3.3 Relation between Coil Overlap Concentration, c*, and Intrinsic Viscosity 392

9.4 Measurement of Viscosity 393

      9.4.1 Poiseuille Equation and Capillary Viscometers 393

      9.4.2 Concentric Cylinder Viscometers 397

9.5 Diffusion Coefficient and Friction Factor 398

      9.5.1 Tracer Diffusion and Hydrodynamic Radius 399

      9.5.2 Mutual Diffusion and Fick’s Laws 400

9.6 Dynamic Light Scattering (DLS) 406

9.7 Hydrodynamic Interactions and Draining 409

9.8 Size Exclusion Chromatography (SEC) 412

      9.8.1 Basic Separation Process 413

      9.8.2 Separation Mechanism 417

      9.8.3 Two Calibration Strategies 419

      9.8.4 Size Exclusion Chromatography Detectors 422

9.9 Chapter Summary 425

Problems 425

References 437

Further Readings 438

Chapter 10 Networks, Gels, and Rubber Elasticity 439

10.1 Formation of Networks by Random Cross-Linking 439

      10.1.1 Definitions 439

      10.1.2 Gel Point 441

10.2 Polymerization with Multifunctional Monomers 443

      10.2.1 Calculation of the Branching Coefficient 445

      10.2.2 Gel Point 446

      10.2.3 Molecular-Weight Averages 447

10.3 Elastic Deformation 450

10.4 Thermodynamics of Elasticity 452

      10.4.1 Equation of State 452

      10.4.2 Ideal Elastomers 454

      10.4.3 Some Experiments on Real Rubbers 455

10.5 Statistical Mechanical Theory of Rubber Elasticity: Ideal Case 456

      10.5.1 Force to Extend a Gaussian Chain 457

      10.5.2 Network of Gaussian Strands 459

      10.5.3 Modulus of the Affine Gaussian Network 460

10.6 Further Developments in Rubber Elasticity 462

      10.6.1 Non-Gaussian Force Law 463

      10.6.2 Front Factor 465

      10.6.3 Network Defects 466

      10.6.4 Mooney-Rivlin Equation 468

10.7 Swelling of Gels 469

      10.7.1 Modulus of a Swollen Rubber 470

      10.7.2 Swelling Equilibrium 471

10.8 Chapter Summary 474

Problems 475

References 479

Further Readings 479

Chapter 11 Linear Viscoelasticity 481

11.1 Basic Concepts 481

      11.1.1 Stress and Strain 483

      11.1.2 Viscosity, Modulus, and Compliance 483

      11.1.3 Viscous and Elastic Responses 484

11.2 Response of the Maxwell and Voigt Elements 485

      11.2.1 Transient Response: Stress Relaxation 485

      11.2.2 Transient Response: Creep 487

      11.2.3 Dynamic Response: Loss and Storage Moduli 489

      11.2.4 Dynamic Response: Complex Modulus and Complex Viscosity 492

11.3 Boltzmann Superposition Principle 493

11.4 Bead-Spring Model 494

      11.4.1 Ingredients of the Bead-Spring Model 495

      11.4.2 Predictions of the Bead-Spring Model 496

11.5 Zimm Model for Dilute Solutions, Rouse Model for Unentangled Melts 502

11.6 Phenomenology of Entanglement 506

      11.6.1 Rubbery Plateau 506

      11.6.2 Dependence of Me on Molecular Structure 509

11.7 Reptation Model 513

      11.7.1 Reptation Model: Longest Relaxation Time and Diffusivity 513

      11.7.2 Reptation Model: Viscoelastic Properties 517

      11.7.3 Reptation Model: Additional Relaxation Processes 519

11.8 Aspects of Experimental Rheometry 520

      11.8.1 Shear Sandwich and Cone and Plate Rheometers 521

      11.8.2 Further Comments about Rheometry 522

11.9 Chapter Summary 523

Problems 524

References 531

Further Readings 531

Chapter 12 Glass Transition 533

12.1 Introduction 533

      12.1.1 Definition of a Glass 533

      12.1.2 Glass and Melting Transitions 534

12.2 Thermodynamic Aspects of the Glass Transition 536

      12.2.1 First-Order and Second-Order Phase Transitions 537

      12.2.2 Kauzmann Temperature 539

      12.2.3 Theory of Gibbs and DiMarzio 540

12.3 Locating the Glass Transition Temperature 542

      12.3.1 Dilatometry 542

      12.3.2 Calorimetry 544

      12.3.3 Dynamic Mechanical Analysis 546

12.4 Free Volume Description of the Glass Transition 547

      12.4.1 Temperature Dependence of the Free Volume 547

      12.4.2 Free Volume Changes Inferred from the Viscosity 549

      12.4.3 Williams—Landel-Ferry Equation 551

12.5 Time-Temperature Superposition 553

12.6 Factors that Affect the Glass Transition Temperature 559

      12.6.1 Dependence on Chemical Structure 559

      12.6.2 Dependence on Molecular Weight 559

      12.6.3 Dependence on Composition 560

12.7 Mechanical Properties of Glassy Polymers 563

      12.7.1 Basic Concepts 564

      12.7.2 Crazing, Yielding, and the Brittle-to-Ductile Transition 566

      12.7.3 Role of Chain Stiffness and Entanglements 568

12.8 Chapter Summary 572

Problems 572

References 580

Further Readings 580

Chapter 13 Crystalline Polymers 581

13.1 Introduction and Overview 581

13.2 Structure and Characterization of Unit Cells 583

      13.2.1 Classes of Crystals 583

      13.2.2 X-ray Diffraction 584

      13.2.3 Examples of Unit Cells 587

13.3 Thermodynamics of Crystallization: Relation of Melting Temperature to Molecular Structure 590

13.4 Structure and Melting of Lamellae 595

      13.4.1 Surface Contributions to Phase Transitions 595

      13.4.2 Dependence of Tm on Lamellar Thickness 596

      13.4.3 Dependence of Tm on Molecular Weight 600

      13.4.4 Experimental Characterization of Lamellar Structure 601

13.5 Kinetics of Nucleation and Growth 605

      13.5.1 Primary Nucleation 606

      13.5.2 Crystal Growth 610

13.6 Morphology of Semicrystalline Polymers 614

      13.6.1 Spherulites 614

      13.6.2 Nonspherulitic Morphologies 618

13.7 Kinetics of Bulk Crystallization 620

      13.7.1 Avrami Equation 621

      13.7.2 Kinetics of Crystallization: Experimental Aspects 626

13.8 Chapter Summary 630

Problems 631

References 638

Further Readings 638

Appendix 639

Index 647

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